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WO2006109815A1 - Condensateur électrique double couche - Google Patents

Condensateur électrique double couche Download PDF

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Publication number
WO2006109815A1
WO2006109815A1 PCT/JP2006/307688 JP2006307688W WO2006109815A1 WO 2006109815 A1 WO2006109815 A1 WO 2006109815A1 JP 2006307688 W JP2006307688 W JP 2006307688W WO 2006109815 A1 WO2006109815 A1 WO 2006109815A1
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WIPO (PCT)
Prior art keywords
acid
activated carbon
electric double
dimethyl
group
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PCT/JP2006/307688
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English (en)
Japanese (ja)
Inventor
Tamon Itahashi
Masahito Sekiguchi
Taketoshi Kikuchi
Naoki Inui
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Sumitomo Chemical Company, Limited
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Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to EP06731635A priority Critical patent/EP1876611A4/fr
Publication of WO2006109815A1 publication Critical patent/WO2006109815A1/fr
Priority to US11/907,119 priority patent/US7800886B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an electric double layer capacity.
  • An electric double layer capacitor consists of an electrode, a separator, and an electrolyte.
  • the electrolyte dissolved in the electrolyte is adsorbed by the electrode and formed on the interface (electric double layer) formed between the electrolyte and the electrode.
  • the energy stored is expressed as 1Z2 'C' V 2 (where C is the capacitance (F) and V is the electric potential).
  • C the capacitance (F) and V is the electric potential).
  • the capacitance of the electric energy storage device In order to store a large amount of electrical energy in a compact tank, it is required to improve the capacitance per unit volume.
  • Activated carbon is widely used as an electrode for electric double-layer capacitors, and specific examples include activated carbon mainly composed of micropores (pore diameter 2 OA or less) obtained by carbonizing and activating raw materials such as coconut shells.
  • US Pat. No. 48732 18 (Table 1) shows that the molar ratio (R / C) of resorcinol (R) to basic catalyst (C) is 20 0 to 4 10 times, and resorcinol (R)
  • R An organic air-mouthed gel activated carbon obtained by polymerization with a weight ratio (R / W) of water to an aqueous solvent (W) of 0.02 to 0.067 times is disclosed. No.
  • resorcinol and formaldehyde are polymerized in the presence of a basic catalyst and an aqueous solvent to obtain an organic air gel having uniform mesopores (pore diameter of 2 OA or more), and then washed with an organic solvent.
  • the mesopore-based activated carbon obtained by substituting the aqueous solvent with the organic solvent, dried and subsequently carbonized is known as an electrode for an electric double layer capacitor having a large capacitance per unit weight. It is disclosed that it can be used (see Japanese Patent Laid-Open No. 9-328308 ([00 17]), Special Publication 2002-5 11 899 (p 35)).
  • Japanese Patent Laid-Open No. 9-328308 ([00 1 7]) uses tetraethylammonium salt as an electrolyte, and JP 2002-511 899 (p 3 5) uses potassium hydroxide as an electrolyte.
  • JP 2002-511 899 (p 3 5) uses potassium hydroxide as an electrolyte.
  • an aqueous electrolyte such as potassium hydroxide
  • the inventors of the present invention have studied the electric double layer capacitor described in Japanese Patent Application Laid-Open No. 9-328308 ([00 1 7]). As a result, it is clear that the electrostatic capacity per unit volume cannot be obtained sufficiently. became.
  • an electric double layer capacitor containing a certain type of electrolyte is an electric double layer capacitor containing a certain type of activated carbon per unit volume. We found that the capacitance was improved. Disclosure of the invention
  • An object of the present invention is to provide an electric double layer capacity having an improved capacitance per unit volume. That is, the present invention provides the following [1] to [12].
  • R and R ′ each independently represent an alkyl group having 1 to 6 carbon atoms; R 1 to R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X— represents counter ion)
  • An organic air mouth gel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. Electric double layer capacity is an activated carbon obtained in this way.
  • Activated carbon is activated carbon obtained by using 0.25 to 1 000 moles of phenolic compound per mole of basic catalyst and 0.5 to 5 parts by weight of phenolic compound per 1 part by weight of aqueous solvent.
  • Activated carbon is activated carbon obtained by carbonization at 650-850 [1]
  • [1 1] Method for producing activated carbon by polymerizing a phenolic compound and an aldehyde compound having at least one hydroxyl group in the molecule in the presence of an aqueous solvent and a basic catalyst, and carbonizing the obtained organic aerogel
  • a phenolic compound is polymerized using 0.25 to 1,000 moles of phenolic compound per mole of the basic catalyst and 0.5 to 5 parts by weight of phenolic compound per 1 part by weight of the aqueous solvent.
  • the electric double layer capacitor of the present invention comprises an electrode made of activated carbon, an electrolyte containing an electrolyte, and a separator.
  • the electrolyte used in the present invention is an imidazolinium salt represented by the formula (1).
  • R and R ′ each independently represents an alkyl group having about 1 to 6 carbon atoms.
  • the alkyl group having about 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Of these, a methyl group and an ethyl group are preferable because the electrostatic capacity per unit volume tends to increase.
  • R 1 to R 3 each independently represents a hydrogen atom or an alkyl group having about 1 to 6 carbon atoms. Examples of the alkyl group having about 1 to 6 carbon atoms are the same as those described above. R 1 to R 3 may be groups different from each other.
  • imidazolium cation examples include 1,3-dimethylimidazole, 1 dimethyl 3-methylimidazole, 1,3-jetylimidazole, 1,2,3-trimethylimidazole, 1, 3, 4--trimethylimidazolium, 1-ethyl-2-, 3-dimethyldimethyl, 1-ethyl-3, 4-dimethylimidazole, 1-ethyl-3,5-dimethylimidazole, 2-ethyl-1, 3 —Dimethylimidazolium, 4-ethylyl 1,3-dimethyl imidazolium, 1,2-jetyl 3-methylimidazole, 1,4 monojetyl 3-methylimidazole, 1,5-jetyl 3-methylimid Dazolium, 1, 3—Jetyl—2—Methylimidazolium, 1,3—Jetchiru 4-Methylimidazolium, 1,2,3—Triedylimidazolium, 1, 3, 4— Lietil imidazolium
  • the electrolyte cation used in the electric double layer capacitor according to the present invention includes tetraethyl ammonium, triethylmethyl ammonium, trimethylpropyl ammonium, 1-ethyl 1-methylpyrrolidinium, 1 methyl 1 1 1 Aliphatic quaternary ammonium cations such as propirpiperidinium may be included.
  • the electrolyte counterions used in the electric double layer capacitor of the present invention are usually BF 4 —, PF 6 —, C 1 0 4 —, N (CF 3 S 0 2 ) —, CF 3 C 0 2 — etc. Among them, CF 3 C0 2 — and BF 4 ⁇ are preferable because the electrostatic capacity per unit volume tends to increase.
  • the counter ion may be a mixture of different types of anions.
  • a polar solvent is usually used, and examples of the solvent include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, jetyl carbonate, diphenyl carbonate, and methyl phenyl carbonate;
  • Carbonates such as cyclic carbonates such as ethylene carbonate, propylene carbonate, 2,3-dimethylethylene carbonate, butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate;
  • Carboxylic acids such as methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl benzoate, ethyl benzoate, Ryoichi ⁇ -lacton, valerolacton, ⁇ -valerolacton Esters; ethylene glycol dimethyl ether, ethylene glycol jetyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether — ter, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, 2-methyltetrahydrofuran, 2, 6— Ethers such as dimethyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile, propionitryl, methoxypropionitryl, glutaronitrile, adiponitrile, 2-methyldaltalonit
  • Sulfones such as dimethylsulfone, ethylmethylsulfone, jetylsulfone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane;
  • Sulfoxides such as dimethylsulfoxide, methylethylsulfoxide, jetylsulfoxide; dimethyl sulfate, sulfuric acid Sulfates such as jetyl, ethylene sulfate, propylene sulfate;
  • the solvent for dissolving the electrolyte may be a mixture of different solvents.
  • the solvent for dissolving the electrolyte carbonic acid esters, carboxylic acid esters, nitriles, amides and sulfones are preferably used, and carbonic acid esters and strong rubonic acid esters are more preferably used.
  • the concentration of the electrolyte in the electrolyte is usually 0.5 to 5.
  • Omo 1 (electrolyte) L (electrolyte). is there.
  • the water content contained in the electrolytic solution is usually 200 ppm or less, preferably 50 ppm or less, and more preferably 20 ppm or less. By suppressing the water content, it is possible to avoid the influence on the electrode due to the electrolysis of water, in particular, the reduction of the withstand voltage.
  • the activated carbon used in the present invention carbonizes an organic air-mouthed gel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. It is the activated carbon obtained.
  • the phenolic compound is a phenolic compound having at least one hydroxyl group in the molecule, and specifically, a compound represented by the formula (3) is exemplified.
  • R 1 G represents an alkyl group having about 1 to 12 carbon atoms to which a substituent may be bonded.
  • R 1 Q is a plurality may be R 1 Q are different from each other.
  • n represents an integer of 0 to 3
  • m represents an integer of 2 to 5. However, the sum of n and m is 5 or less.
  • Examples of the substituent which may be bonded to the alkyl group include, for example, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, a strong rubamoyl group, a carboxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and Examples thereof include a sulfamoyl group.
  • R ′ 0 may be linear, branched or cyclic. Is then R '0, for example, a methyl group, Echiru group, n- propyl group, i one propyl Le group, n- butyl group, i - butyl, s - butyl group, n- old corruptible group, nonyl group, p—t an alkyl group such as a monobutyl group;
  • An alkyl group to which cyano is bonded such as cyanomethyl group, 2-cyanoethyl group, or 3-cyanopropyl group;
  • Alkoxy groups such as methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group
  • Halogenated alkyl groups such as chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl; Poxymethyl group, 2—Strong loxychetyl group, 3 —Carboxypropyl group,
  • the number of carbons in R IQ is usually about 1 to 12.
  • R 10 is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-octyl group.
  • n is preferably 3 or 4, more preferably 4.
  • m 1 or 2 is preferable, and 1 is more preferable.
  • Specific examples of the compound represented by the formula (3) include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,
  • the phenolic compounds may be used alone or in admixture of two or more.
  • the phenolic compound it is particularly preferable to use resorcinol or phloroglucinol.
  • aldehyde compound used in the production of the organic air mouth gel include formaldehyde, paraformaldehyde, acetoaldehyde, butyl aldehyde, salicylaldehyde, benzaldehyde and the like. Of these, formaldehyde is preferably used.
  • the amount of the aldehyde compound to be used is usually about 1 to 3 mol, preferably about 1.2 to 2.5 mol, per 1 mol of the phenolic compound.
  • Examples of basic catalysts used in the production of organic air-mouth gel include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium carbonate, sodium phosphate, lithium phosphate, Examples include potassium phosphate. Of these, sodium carbonate is preferably used.
  • the amount ratio of the basic catalyst to the phenolic compound is usually 0.25 to 100,000 moles, preferably 0.25 to 100 moles of the phenolic compound per mole of the basic catalyst. The range is 0 mol, and more preferably in the range of 1 to 500 mol.
  • the phenolic compound is in the range of from 0.25 to I100,000 with respect to the basic catalyst because the capacitance tends to be improved.
  • the aqueous solvent used in the production of the organic air-mouthed gel means water, an organic solvent that can be mixed with water at an arbitrary ratio, and a mixture of the organic solvent and water.
  • Specific examples of the organic solvent include alcohol solvents such as methanol, ethanol and i-propyl alcohol, and ether solvents such as tetrahydrofuran. These solvents may be used alone or in combination of two or more.
  • aqueous solvent water, an alcohol solvent having 3 or less carbon atoms, a mixture of water and an alcohol solvent having 3 or less carbon atoms is preferably used, and water is more preferably used.
  • the amount ratio of the aqueous solvent to the phenolic compound is usually 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight, with respect to 1 part by weight of the aqueous solvent.
  • the amount ratio of the aqueous solvent to the phenolic compound is preferably 0.5 to 5 parts by weight because the electrostatic capacity per unit volume tends to be improved.
  • the use amount of the aqueous solvent means the use amount of the aqueous solvent at the time of polymerization, so the aqueous solvent contained in the phenolic compound or the aldehyde compound is also included in the use amount.
  • the aqueous solvent contained in the phenolic compound or the aldehyde compound is also included in the use amount.
  • aqueous solvent for example, in the case of a 37% formalin aqueous solution, 63% water is calculated as an aqueous solvent.
  • a method for producing an organic air-mouth gel for example, a phenolic compound, an aldehyde compound, a basic catalyst, and an aqueous solvent are mixed together, and usually 0 to 100: preferably 30 to 9.
  • An aldehyde compound is mixed with a mixture comprising a phenolic compound, a basic catalyst and an aqueous solvent, usually at 0 to 100, preferably ⁇ 30 to 90 to obtain a wet gel, and then dried.
  • Method A method in which a phenolic compound is mixed with a mixture comprising an aldehyde compound, a basic catalyst and an aqueous solvent, usually at 0 to 100 t: preferably 30 to 90 to obtain a wet gel and then dried.
  • a basic catalyst is mixed with a mixture of a phenolic compound, an aldehyde compound and an aqueous solvent, usually at 0 to 100 t: preferably 30 to 90 to obtain a wet gel and then dried.
  • the method etc. are mentioned.
  • a method of obtaining a wet gel by mixing an aldehyde compound with a mixture comprising a phenolic compound, a basic catalyst and an aqueous solvent is preferable.
  • the drying of the wet gel include a method of ventilating at room temperature to about 100 "C or drying under reduced pressure. Also, when the solvent in the wet gel is water, it is replaced with a hydrophilic organic solvent. Then, ventilate at room temperature to about 100 or dry under reduced pressure.
  • hydrophilic organic solvent examples include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and t-butyl alcohol; aliphatic nitriles such as acetonitrile; aliphatic ketones such as aceton; Aliphatic sulfoxides such as dimethyl sulfoxide; and aliphatic carboxylic acids such as acetic acid.
  • alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and t-butyl alcohol
  • aliphatic nitriles such as acetonitrile
  • aliphatic ketones such as aceton
  • Aliphatic sulfoxides such as dimethyl sulfoxide
  • aliphatic carboxylic acids such as acetic acid.
  • hydrophilic organic solvent t-butyl alcohol, dimethyl sulfoxide, and acetic acid are preferably used, and t-butyl alcohol is particularly preferable because it can be easily replaced with water.
  • freeze-dried instead of the method of ventilating at room temperature to about 100 or drying under reduced pressure.
  • the temperature in freeze-drying is usually in the range of ⁇ 70 to 203 ⁇ 4: preferably in the range of 30 to 10 °.
  • lyophilization is usually performed under vacuum.
  • drying may be performed under supercritical conditions using carbon dioxide or the like.
  • the activated carbon used in the present invention can be obtained by carbonizing and activating an organic air mouth gel obtained by drying.
  • the specific method for producing the activated carbon is as follows: (I) In a gas atmosphere inert to carbon such as nitrogen, argon, helium, hydrogen, etc., usually in the range of 200 to 150 Ot, preferably 600 to 110 "at the C range, usually, after 1 minute to about 24 hours baking (carbonization), H 2 0, in the presence of C_ ⁇ 2, 0 2, etc.
  • oxidizing gas typically at 200 to 1 500 In the range, preferably in the range of 600 to 1100, and usually firing (activation) for about 1 minute to 10 hours;
  • (II) in the presence of oxidizing gas usually in the range of 200 to 1500 Calcination (carbonization and activation), usually in the range of 600 to 110 O: for about 1 minute to 24 hours;
  • Compound (1) in the presence of an oxidizing gas such as air it is usually 400 or less, preferably 200 to 300, usually after firing (carbonization) for about 1 minute to 24 hours, and then in a gas atmosphere inert to carbon.
  • 200 to 1 50 Ot range, preferably at a range of at 600-1 1 00, usually 1 minute to about 24 hours calcined (carbonized), further, in the presence of an oxidizing gas, typically, 200 W 200
  • the methods (I) to (V) are preferable because they do not contain a metal. Further, as the oxidizing gas, H 2 0 and 0 2 are preferable.
  • the activated carbon used in the present invention preferably has a pore volume of 1.5 cc or less, more preferably 0.1 to: 1.5 c cZg, and still more preferably 0.3 to 1.0 c. cZg, particularly preferably 0.3 to 0.6 cc / g.
  • the pore volume of the activated carbon is 1.5 c cZg or less because the electrostatic capacity per unit volume tends to be improved.
  • the imidazolinium salt described above is preferably used as the electrolyte, but is generally used.
  • An electrolyte may be used.
  • Examples of electrolytes commonly used other than the imidazolinium salt (1) include salts containing an organic quaternary ammonium cation having 4 to 12 carbon atoms, among others, anion and organic quaternary ammonium cation.
  • the salt consisting of is preferably used.
  • electrolyte for example, B0 3 3 -, F-, PF 6 -, BF 4 -, A s F 6 -, S b F 6 -, C L_ ⁇ 4 -, A 1 F 4 - , A 1 C 1 4 -, T a F, n b F 6 -, S i F 6 2 -, CN- later, (in the formula, n represents a number from 1 to 4) F (HF) n and inorganic Anion such A combination of an organic anion and an organic cation described later, and a combination of an organic anion and an inorganic force thione such as a lithium ion, a sodium ion, a potassium ion, or a hydrogen ion.
  • Organic cation is a cationic organic compound, for example, organic quaternary ammonia Nium cations and organic quaternary phosphonium cations.
  • Organic quaternary ammonium cations are alkyl groups (1 to 20 carbon atoms), alkyl groups (6 to 20 carbon atoms), aryl groups (6 to 20 carbon atoms) and aralkyl groups (carbon atoms).
  • a quaternary ammonium cation in which a hydrocarbon group selected from the group consisting of 7 to 20) is replaced by a nitrogen atom, and an organic quaternary phosphonium catalyst is the same hydrocarbon as described above.
  • a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, an ether group, an aldehyde group, or the like may be bonded to the substituted hydrocarbon group.
  • X represents a nitrogen atom or a phosphorus atom
  • n and m each independently represents an integer of 4 to 6.
  • N N-dimethylbiveridinium, N-ethyl-N-methylbiperidinium, N, N-jetylbiperidinium, N-n-propyl mono-N-methylbiperidinium, N-n-butyl-N-methylbiveridi Nyum, N—Etilu N—n—Butylpiperidinum, etc.
  • N, N, N ', N'-tetramethylpiperazinium N—ethylil N, N', ⁇ '-trimethylpiperazinum, ⁇ , N'-jetyl- ⁇ , N'-dimethyl piperazinum, ⁇ , ⁇ , N '— Triethylou N' — Methylbiperazinum, ⁇ , ⁇ , ⁇ ', N' — Tetraethylpiperazinum, etc.
  • 1,3-Dimethyl-1,4-, or 1,6-Dihydropyrimidinium [These are expressed as 1,3-Dimethyl-1,4 (6) -Dihydropyrimidinium, and so on. Is used. ] 1, 2, 3— Trimethyl-1, 4, 4 (6) Dihydropyrimidinum, 1, 2, 3, 4-tetramethyl-1, 4, (6) Monodihydric pyrimidinium, 1, 2, 3, 5-tetramethyl 1, 4 (6) —Dihydropyrimidinium, 8-methyl-1,8-diazabicyclo [5, 4, 0]-7, 9 (1 0) Undecadienum, 5-methyl-1,1,5-diazabicyclo [4 , 3, 0] 1, 5, 7 (8) -Nonagenium, 4-Cyanol 1, 2, 3—Trimethyl 1,1,4 (6) —Dihydropyrimidinium, 3-Cyanmethyl-1,2,2-dimethyl 1,4 ( 6) —Dihydropyrimidinium, 2-Cyanomethyl
  • N-methylpicolinium N-ethylpicolinium, etc.
  • N-methyl quinolinium N-ethyl quinolinium, etc.
  • R f represents a perfluoroalkyl group having 1 to 12 carbon atoms
  • examples include anions, and the following organic acids (carboxylic acid, organic sulfonic acid, organic phosphoric acid) or anions obtained by removing active hydrogen atoms from phenol. (carboxylic acid) .
  • polycarboxylic acid • 2 to 15 carbon divalent or tetravalent polycarboxylic acid: aliphatic polycarboxylic acid [saturated polycarboxylic acid (succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, spellin
  • Acid azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pendedecanedioic acid, hexadecanedioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, Pentylmalonic acid, Hexylmalonic acid, Dimethylmalonic acid, Jetylmalonic acid, Methylpropylmalonic acid, Methylbutylmalonic acid, Ethylpropylmalonic acid, Dipropylmalonic acid, Methylsuccinic acid, Ethylsuccinic acid, 2,2-Dimethylsuccinic acid, 2, 3-Dimethylsuccinic acid, 2-Methylglutaric acid, 3-Methylglutaric acid, 3-Methyl-3-Ethyldalta
  • 3-dicarboxylic acid bicyclo [2, 2, 1] hep 2,2,5-gen- 2,3-dicarboxylic acid, 1-methyl mono-bicyclo [2, 2, 1] hep 2,2,5-gen 2 , 3-Dicarboxylic acid, 6-Methylbicyclo [2, 2, 1] Hep Yui 2 '5-Gen 1,2,3-Dicarboxylic acid, Furan 1,3-Dicarboxylic acid, 5-Methyl-furan 1,2, 3 —Dicarboxylic acid, 4-methyl-furan-1,3-dicarboxylic acid.
  • cyclobutene 1,1,2-dicarboxylic acid 4-methyl-cyclobutene 1,1,2-dicarboxylic acid, cyclopentene 1,2-dicarboxylic acid, 5-methyl-cyclopentene 1,2-dicarboxylic acid Acid, bicyclo [2,2,1] hepter 2-en-2,3-dicarboxylic acid, bicyclo [2,2,1] hep2-1,5-dicarboxylic acid 2,3-dicarboxylic acid, furanic acid 2 , 3-Dicarboxylic acid, 5-Methyl-furan 1,2,3-Dicarboxylic acid, 4-Methyl-furan-2, 3-Dicarboxylic acid, 5-Methyl-2,3-Furandicarboxylic acid, 4,5-Dihydroxy-furan 1 , 3-dicarboxylic acid, 2,5-dihydroxy-furan-1,3,4-dicarboxylic acid, maleic acid, fumaric acid, itaconic acid
  • 1,2-cyclobutadiene is preferred.
  • 1,2-dicarboxylic acid 4-monomethyl-1,2-cyclobutadiene-1,2-dicarboxylic acid, 1,2-cyclopentadiene 1,2-dicarboxylic acid, 5-methyl-1,2-cyclopentene Gen 1,2-dicarboxylic acid, furan 3,4-dicarboxylic acid, 2-methyl-3,4-furan-dicarboxylic acid, etc.]
  • aromatic polycarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, trimellit Acid, pyromellitic acid, etc.], S-containing polycarboxylic acid [thiodibropionic acid, etc.];
  • Oxycarboxylic acid having 2 to 20 carbon atoms Aliphatic oxycarboxylic acid [Daricol acid, lactic acid, tartaric acid, castor oil fatty acid, etc.]; Aromatic oxycarboxylic acid [salicylic acid, mandelic acid, 4-hydroxybenzoic acid, 1-hydroxy-2-naphtho Acid, 3-hydroxy-1-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, etc.];
  • Monocarboxylic acid having 1 to 30 carbon atoms aliphatic monocarboxylic acid [saturated monocarboxylic acid (formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, cabronic acid, enanthic acid, strong prillic acid, pelargon Acid, urallylic acid, myristic acid, stearic acid, behenic acid, undencanic acid, etc.), unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, crotonic acid, oleic acid, squaric acid, 4,5-dihydroxy 1 4 — Cyclopentene 1,3-dione, 2,3-dihydroxy-2-cyclohexene-1,4-dione, etc.]]; Aromatic monocarboxylic acid [benzoic acid, cinnamate, naphthoic acid, toluic acid, ethylbenzoate Acid, propy
  • Monovalent phenols including phenols and naphthols: phenols, alkyls (1 to 15 carbon atoms) phenols (Klepur, xylenol, edylphenol, n- or isopropylphenol, isododecylphenol, etc.) , Methoxyphenols (eugenol, guaiacol, etc.), ⁇ -naphthol, 3-naphthol, cyclohexylphenol, etc .;
  • Multivalent phenol Catechol, resorcin, pyrogallol, phloroglucin, bisphenol ⁇ ⁇ ⁇ , bisphenol F, bisphenol S, etc.
  • Mono and dimethyl phosphate esters Mono and disopropyl phosphate esters, mono and dibutyl phosphate esters, mono and di- (2-ethylhexyl) phosphate esters, mono and diisodecyl phosphate esters, and the like.
  • Organic sulfonic acid Organic sulfonic acid
  • Alkyl (1 to 15 carbon atoms) benzenesulfonic acid (P-toluenesulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc.), sulfosalicylic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.
  • Triazole an organic acid having a tetrazol skeleton
  • Polodisuccinic acid porodiglycolic acid, porodi (2-hydroxyisobutyric acid), alkaneboric acid, arylboric acid, methaneboric acid, diboronic acid, phenylphosphoric acid, etc.
  • R ′ represents a hydrocarbon having 1 to 10 carbon atoms which may have a hydroxyl group, an amino group, a nitro group, a cyano group, a chloro group, a fluoro group, a formyl group or a group having an ether bond.
  • R ′ may be the same or different from each other, and R ′ may be bonded to each other as an alkylene group to form a ring.
  • R represents the same meaning as R '.
  • R may be the same as or different from each other.
  • R may be bonded to each other as a hydrocarbon group to form a ring.
  • R 1 and R 2 are monovalent organic groups having 1 to 4 carbon atoms and containing fluorine. R 1 and R 2 may be the same or different from each other. R 3 is 2 to 2 carbon atoms. . 8 is a divalent organic group containing fluorine) the Anion, inorganic Anion is preferable,, BFA s F 6 one, S b F 6 - are preferable, among others, BF 4 - is, electrostatic This is preferable because the capacity tends to increase.
  • the electrolytic solution containing an organic electrolyte a solvent containing an organic polar solvent as a main component is used, and the content of water contained in the electrolytic solution containing an organic polar solvent is usually 20 Oppm or less, preferably 50 ppm or less, more preferably 20 ppm or less.
  • the solvent of the electrolytic solution for dissolving the electrolyte the same one as that used for the imidazolinium cation is used.
  • Examples of the concentration of the electrolyte in the electrolytic solution include the same concentration as that used for the imidazolium cation.
  • Examples of methods for using the activated carbon thus obtained as an electrode for an electric double layer capacitor include, for example, a method in which carbon is used as it is, a method in which activated carbon is broken, a method in which crushed activated carbon is produced.
  • Examples of the method include molding into various shapes such as granules, granules, fibers, felts, fines, and sheets.
  • the particle size of the activated carbon particles used in the molding method is usually pulverized to an average particle size of 50 m or less, preferably 30 m or less, particularly preferably 10 m or less. By finely pulverizing the activated carbon, the bulk density of the electrode can be improved and the internal resistance can be reduced.
  • powdering methods include impact friction crushers, centrifugal crushers, pole mills ( Pulverizers for fine powder such as tube mills, compound mills, conical ball mills, rod mills), vibration mills, colloid mills, friction disk mills, and jet mills are preferably used.
  • the electrode of the present invention is an electrode characterized by containing the activated carbon. Usually, the electrode further contains a binder, a conductive agent and the like so as to be easily formed as an electrode.
  • a mixture containing activated carbon, a binder, a conductive agent, etc. is usually formed on a current collector.
  • a mixed slurry in which a solvent is added to activated carbon, a binder, a conductive agent, etc. is applied to a current collector or dipped by a doctor blade method or the like, and dried, for example, activated carbon, a binder, conductive
  • the thickness is about 50 to 100; m.
  • current collector materials include metals such as nickel, aluminum, titanium, copper, gold, silver, platinum, aluminum alloys, and stainless steel, such as carbon materials, activated carbon fibers, nickel, aluminum, zinc, copper, Films formed by plasma spraying or arc spraying of tin, lead, or their alloys, for example, conductive films in which a conductive agent is dispersed in a resin such as rubber, styrene-ethylene-butylene-styrene copolymer (SEBS), etc. Etc.
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • Aluminum that is particularly lightweight, excellent in electrical conductivity, and electrochemically stable is preferable.
  • the shape of the current collector for example, a foil, a flat plate, a mesh, a net, a lath, a punching or an embossed shape, or a combination thereof (for example, a mesh flat plate) Etc.
  • Concavities and convexities may be formed on the surface of the current collector by etching.
  • the conductive agent include graphite, carbon black, acetylene black, ketjen black, and conductive carbon such as activated carbon different from the present invention; graphite-based conductive materials such as natural graphite, thermally expanded graphite, scaly graphite, and expanded graphite.
  • Carbon fibers such as vapor-grown carbon fibers; Metal fine particles or metal fibers such as aluminum, nickel, copper, silver, gold, platinum; Conductive metal oxides such as ruthenium oxide or titanium oxide; Polyaniline, Polypyrrole And conductive polymers such as polythiophene, polythiophene, polyacetylene, and polyacene.
  • Carbon black, acetylene black and ketjen black are particularly preferred in that the conductivity is effectively improved with a small amount.
  • the compounding amount of the conductive agent in the electrode is usually about 5 to 50 parts by weight, preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the activated carbon of the present invention.
  • the binder include a polymer of a fluorine compound, and a fluorine compound.
  • binders include addition polymers of monomers containing an ethylenic double bond that does not contain a fluorine atom.
  • Examples of such monomers include (cyclo) alkyl (carbon number 1 ⁇ 2 2) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i so-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, etc.]; aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate, phenethyl (meth) acrylate Etc.]; alkylene glycol or dialkylene glycol Mono (meth) acrylate of alkylene group having 2 to 4 carbon atoms [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (me
  • the addition polymer may be a copolymer composed of a plurality of types of monomers such as an ethylene / vinyl acetate copolymer, a styrene / butadiene copolymer, and an ethylene / propylene copolymer.
  • the carboxylic acid vinyl ester polymer may be partially or completely saponified, such as polyvinyl alcohol.
  • the conjugate may be a copolymer of a fluorine compound and a monomer containing an ethylenic double bond not containing a fluorine atom.
  • binders include, for example, polysaccharides such as starch, methylcellulose, strong rupoxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, strong lpoxymethylhydroxyethylcellulose, and nitrocellulose and the like. Derivatives; Phenolic resins; Melamine resins; Polyurethane resins; Urea resins: Polyimide resins; Polyamideimide resins; Petroleum pitches;
  • binder among these, a polymer of a fluorine compound is preferable, and in particular, polytetrafluoroethylene which is a polymer of tetrafluoroethylene is preferable.
  • binder a plurality of types of binders may be used. .
  • the compounding amount of the binder in the electrode is usually about 0.5 to 30 parts by weight, preferably about 2 to 30 parts by weight with respect to 100 parts by weight of the activated carbon.
  • the solvent used for the binder examples include IPA (isopropyl alcohol), alcohols such as ethanol and methanol, ethers, and ketones. If the binder thickens, a plasticizer may be used to facilitate application to the current collector.
  • the conductive adhesive is usually a mixture of the conductive agent and the binder, and among them, the mixture of the force pump rack and polyvinyl alcohol does not require the use of an organic solvent, and is easy to prepare.
  • the electrode of the present invention is suitable because it is excellent in storage stability.
  • the electrode of the present invention is used for an electrode of a dry battery, a redox capacitor, a hybrid capacitor, an electric double layer capacitor, or the like.
  • redox capacity is described in, for example, Chapter 3 (p 1 4 1-) of "The Forefront of Large-Capacity Double-Layer Capacitors (Supervised by Hideo Tamura, Publisher Nichi Tis S)"
  • a device is characterized in that an active material is contained in an electrode, and electricity is stored by an oxidation-reduction reaction.
  • a separator similar to that used in the electric double layer capacitor described later is sandwiched between the two electrodes to fill the electrolyte.
  • the electrolytic solution is a mixture of an electrolyte and a solvent. means.
  • Examples of active materials used in redox capacitors include transition metal oxides such as ruthenium, transition metal hydroxides, and conductive polymers.
  • the electrode contains 1 to 60% by weight of the activated carbon of the present invention alone or a mixture of the activated carbon of the present invention and the conductive agent exemplified above, and 2 to 30% by weight of the binder exemplified above.
  • a transition metal oxide such as ruthenium or a transition metal hydroxide
  • an aqueous sulfuric acid solution may be used under the conditions described in US Pat.
  • an organic acid is used as the electrolyte and an electrolytic solution dissolved in an organic solvent is used, for example, the application of the conditions described in Japanese Patent Application Laid-Open No. 2 0 2-2 6 7 8 60 may be applied.
  • an electrolyte that dissolves in an organic solvent and dissociates may be used.
  • Li PF 6 because it has a high degree of ionization and good solubility.
  • the concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 1.5 mo 1 ZL because the ionic conductivity is good. If the electrolyte concentration is 0.5 mo 1 ZL or more, the capacitance tends to be improved, and if it is 1.5 mol ZL or less, the viscosity of the electrolyte solution decreases and the ionic conductivity is decreased. This is preferable because of a tendency to improve.
  • an organic polar solvent exemplified in the electric double layer capacitor described later is preferably used.
  • a non-protonic organic solvent for example, a mixed solvent composed of one or more of cyclic carbonate, chain carbonate, cyclic ester and the like can be used.
  • cyclic carbonates include ethylene carbonate and propylene carbonate
  • chain carbonates include dimethyl carbonate, jetyl carbonate, methyl ethyl carbonate
  • examples of cyclic esters include Examples include ptylolactone and r-valerolactone. Any one of these may be used alone, or two or more may be used in combination.
  • the electrolyte solution has a high dielectric constant to promote the dissociation of the electrolyte, a low viscosity so as not to hinder the movement of ions, and a high electrochemical redox resistance. Is required. Therefore, in particular, carbonates are suitable as the solvent. For example, it is possible to use a mixture of ethylene glycol monoponate, etc., as a high dielectric constant solvent, and diphenyl carbonate monotonate, etc., as a low viscosity solvent. desirable.
  • Hybrid capacity means that during charging, lithium ions are inserted in the negative electrode between the layers of black lead, etc. in the negative electrode, and an anion of electrolyte is drawn to the electrode surface in the positive electrode to form an electric double layer.
  • the same electrode as the negative electrode of the lithium ion secondary battery is used for the negative electrode, the electrode of the present invention described above is used for the positive electrode, and the same as the electric double layer capacity described later between the positive electrode and the negative electrode. It is configured to fill the electrolyte with a separator in between.
  • the negative electrode is described in Chapter 1 Section 3 (p. 25-) of “Next-generation lithium secondary battery (supervised by Hideo Tamura, Issuer EN 'Ti' S)”. Something like that can be used.
  • a combination of inorganic canyon and lithium cation is usually used, and in particular, BF 4 —, PF 6 —, CIO
  • a combination of at least one inorganic anion selected from the group consisting of 4 and lithium cathode is preferred.
  • a solvent mainly comprising at least one selected from the group consisting of force and lactones is usually used.
  • specific examples include cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate, chain carbonates such as dimethyl carbonate, ethylmethyl carbonate, and jetyl carbonate, and solvents such as aptilolactone.
  • the additive exemplified in the section of the electric double layer capacity may be used.
  • the electrode of the present invention is suitable for an electrode of an electric double layer capacitor because of its excellent electrostatic capacity.
  • the electric double layer capacity will be described in detail.
  • the electric double layer capacity of the present invention is a capacity characterized by including the electrode. Specifically, for example, the positive electrode that is the electrode. There is a separate separator between the two and the negative electrode, and the capacitor is filled with an electrolyte between the separator and the electrode.
  • the solid electrolyte (the positive electrode and the negative electrode) A capacitor filled with gel electrolyte).
  • the positive electrode By charging, the positive electrode is fully charged, the negative electrolyte forms an electric double layer at the positive electrode interface, and the negative electrode is charged at the same time, and the positive electrolyte forms an electric double layer at the negative electrode interface. Electric energy is stored by Even if charging is stopped, the electric double layer is maintained, but when the battery is discharged, the electric double layer is canceled and electric energy is released.
  • the electric double layer capacity may be a single cell including a positive electrode and a negative electrode, or may be a capacity obtained by combining a plurality of cells.
  • the solid electrolyte is obtained by dispersing an electrolyte described later in a resin, and an organic polar solvent described later may be further dispersed.
  • the electric double layer capacitor according to the present invention has a separate capacitor between the positive electrode and the negative electrode, which are the electrodes, and an electric double layer capacitor filled with an electrolyte between the separator and the electrode. Since evening is suitable, the electric double layer capacitor will be described in detail below.
  • Examples of the shape of the electric double layer capacitor include a coin type, a wound type, a laminated type, and a bellows type.
  • a metal container (1 1) made of stainless steel or the like, a current collector (1 2), an electrode (1 3), a separator (14), an electrode (1 3) and current collector (1 2) are sequentially laminated, filled with electrolyte, and then sealed with a metal lid (15) and gasket (16).
  • a mixed slurry containing the activated charcoal is applied to a current collector (22), dried, and the product of the current collector (22) and the electrode (23) is obtained.
  • a layer sheet is prepared, and the two sheets are wound through a separator (24) and housed in a cylindrical aluminum or stainless steel container (2 1) with an electrode sealing plate (25). Is mentioned.
  • the current collector is provided with a lead in advance, and electricity is charged and discharged using the lead (26) of one laminated sheet as a positive electrode and the lead (26) of the other laminated sheet as a negative electrode.
  • the laminated sheet is made by stacking the current collector (32) and electrode (33) laminated sheets and separator (34) alternately, and then using a metal container such as aluminum or stainless steel (3 1) Put in the electrolyte, fill the electrolyte, and the current collector is alternately connected to the lead (35) and sealed; as shown in Fig. 4, the current collector (4) and electrode (43) Examples include a method of alternately pressing a laminated sheet and a separator (44), sealing an outer layer with a rubber material, filling the electrolyte, and then sealing. Also.
  • the bipolar structure including the gasket (46) as appropriate may be a structure in which the working voltage can be arbitrarily set.
  • a sheet-shaped electrode (53), a separator (54), an electrode (53), a current collector ( 52) and insulating material (55) are stacked, electrolyte solution is filled between the separator (54) and electrode (53), the outer layer is sealed with fluororesin, and bolted with bolts It was carried out at Capashi evening. Porto is insulated from the current collector of (52).
  • the bellows type is a method in which two sheets of an electrode and a current collector are stacked while being folded into a bellows shape via a separator, and then prepared in the same manner as the stacked type.
  • Separators used for electric double-layer capacitors separate the positive and negative electrodes and hold the electrolyte solution. They have a large ion permeability, a predetermined mechanical strength, and an insulating film. Used.
  • the separator may be a molded product made of ceramic powder particles such as silica and the binder.
  • the molded product is usually formed integrally with the positive electrode and the negative electrode.
  • surfactants may be mixed with silica force particles to improve hydrophilicity.
  • the separator evening may contain an organic solvent such as acetone and a plasticizer such as dibutyl phthalate (DBP).
  • DBP dibutyl phthalate
  • a proton conductive polymer may be used as the separator.
  • Separators include, among others, electrolytic paper, viscose rayon or natural cell mouth paper, kraft paper, Manila paper, mixed paper obtained by making cellulose or polyester fibers, polyethylene nonwoven fabric, polypropylene nonwoven fabric, Polyester nonwoven fabric, Manila hemp sheet, glass fiber sheet and the like are preferable.
  • the diameter of the separation night is usually about 0.01 to 10 / im.
  • the thickness of a separate evening is usually.:! About 300 m, preferably about 5-30 m.
  • the separator may be a laminate of separators having different porosity.
  • resorcinol 33.0 g, 37 wt% formalin 48.7 g, sodium carbonate 0.16 g and distilled water 22 g were mixed and kept at 50T: for 24 hours and wetted with water. An organic air mouth gel was obtained.
  • the amount of the phenolic compound used per mole of the base catalyst is 200 mol
  • the amount of the phenolic compound used per 1 part by weight of water is 0. 6 3 parts by weight.
  • the obtained activated carbon had a pore volume of 0.47 cc / g.
  • the activated carbon obtained was pulverized and powdered (mixed with 80 parts by weight, 10 parts by weight of the pump rack and 10 parts by weight of polytetrafluoroethylene, and then into a sheet.
  • Example 1 27.5 g resorcinol, 37% by weight formalin
  • Example 1 the amount of phenolic compound used per 1 part by weight of water (the total amount of water and distilled water contained in formalin) was used as shown in Table 1, and the firing temperature was used as shown in Table 2.
  • Example 1 except that Tetradimethyl ammonium BF 4 salt was used as the electrolyte, the electrolyte was adjusted to 1 mo 1 ZL, and constant current charge / discharge measurement of 3 O mAZg was performed. Conducted in compliance. The results are shown in Table 2. Table 2
  • Example 1 the amount of phenolic compound used per 1 part by weight of water (the total amount of water and distilled water contained in formalin) was used as shown in Table 1, and the firing temperature was used as shown in Table 2.
  • Example 1 except that Tetradimethyl ammonium BF 4 salt was used as the electrolyte, the electrolyte was adjusted to 1 mo 1 / L, and constant current charge / discharge measurement of 3 OmAZg was performed. Conducted in compliance. The results are shown in Table 2.
  • the activated carbon of the present invention bears dry cell electrodes, piezoelectric element sensors, and catalysts. It can be used for holding carriers, chromatographic materials, adsorbents, electrodes for electric double-layer capacitors, etc., and is suitable for electrodes for electric double-layer capacitors because of its excellent capacitance per unit volume. Used for.
  • the electric double layer capacitor of the present invention is excellent in capacitance per unit volume, it can be used for adsorption and storage of energy sources. In particular, due to its excellent characteristics, it can be suitably used for adsorption and storage of energy sources in the field of portable electronic terminals and the field of transport equipment having a charging function.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
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  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne un condensateur électrique double couche comprenant des électrodes constituées d’un charbon actif, une solution électrolytique contenant un électrolyte, et un séparateur, l’électrolyte étant un sel d’imidazolinium, et le charbon actif étant obtenu par polymérisation d’un composé phénolique comportant au moins un groupe hydroxyle dans chaque molécule et un composé aldéhyde en présence d'un solvant aqueux et un catalyseur basique permettant d’obtenir ainsi un aérogel organique et cémentant l’aérogel organique.
PCT/JP2006/307688 2005-04-12 2006-04-05 Condensateur électrique double couche WO2006109815A1 (fr)

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WO2008056554A1 (fr) * 2006-11-09 2008-05-15 Sumitomo Chemical Company, Limited Charbon actif et son procédé de fabrication

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KR101024940B1 (ko) * 2009-02-03 2011-03-31 삼성전기주식회사 표면 산화된 전이금속질화물 에어로젤을 이용한 하이브리드수퍼커패시터
KR101031018B1 (ko) * 2009-02-03 2011-04-25 삼성전기주식회사 전이금속 산화물 에어로젤을 이용한 하이브리드 수퍼커패시터
KR20110080913A (ko) * 2010-01-07 2011-07-13 에스케이케미칼주식회사 초고용량 커패시터용 전해질 용액

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